Polymeric film for water soluble package

ABSTRACT

A water soluble package comprises a polymeric film, the polymeric film comprising a polymeric backbone derived from a polymer which is water soluble, as defined herein, and one or more derivatising groups attached to the backbone, the derivatising group(s) being derived from a material having a ClogP of from 0.5 to 6 and/or being derived from a parent material comprising a C4 to C22 hydrocarbyl chain.

FIELD OF THE INVENTION

[0001] The present invention relates to a polymeric film for a watersoluble package and a water soluble package for containing a fabrictreatment composition, such as a rinse treatment composition.

BACKGROUND AND PRIOR ART

[0002] Rinse added fabric conditioning compositions are well known.Typically, such compositions are provided as a liquid in a plasticsbottle which requires the consumer to dose the correct amount of thefabric softening composition from the bottle into the dispensing drawerof a washing machine.

[0003] The problem with conventional liquid fabric softeners provided ina bottle or other such package is that there is always a risk ofunderdosing or overdosing the rinse conditioning composition into thedispenser drawer of a washing machine resulting in a unsatisfactory orundesired level of softening being provided to fabrics. There is alsothe problem of spillage of the ingredients when pouring the product fromthe package into the dispensing drawer of a washing machine.

[0004] Therefore, it is desirable to provide a rinse conditioningcomposition which is convenient to use and guarantees that the correctamount of fabric softening composition is dosed into the rinse cycle. Itis also desirable to avoid the problem of spillage of the productassociated with the dispensing of conventional rinse conditioners from abottle or the like.

[0005] Water soluble packages are known in the detergent andagrochemical industries and generally comprise either verticalform-fill-seal (VFFS) envelopes or thermoformed envelopes. In one of theVFFS processes, a roll of water soluble film is sealed along its edgesto form a tube, which tube is heat sealed intermittently along itslength to form individual envelopes which are filled with product andheat sealed. The thermoforming process generally involves moulding afirst sheet of water soluble film to form one or more recesses adaptedto retain a composition, such as for example a solid agrochemicalcomposition, placing the composition in the at least one recess, placinga second sheet of water soluble material over the first so as to coverthe or each recess, and heat sealing the first and second sheetstogether at least around the recesses so as to form one or more watersoluble packages.

[0006] Cleaning products are traditionally often liquids, viscous orthin, such as known for personal cleaning (bath and shower liquids andshampoos) or for domestic cleaning (hand dish wash and other hardsurface cleaning, laundry-cleaning etc.). Other products are solids,such as powders, granules, small capsules (up to 2 mm diameter) or morerecently tablets, for laundry and machine dish wash, and soap bars forskin cleaning. Recently, so called unit dose products are experiencingan increasing success with consumers, because they eliminate the needfor manipulating, and possibly spilling, liquids or powders and simplifythe use of a correct dose of the product for the required purpose.Examples thereof are the laundry and machine dish wash tablets mentionedabove and recently described in F. Schambil and M. Böcker, Tenside Surf.Det. 37 (2000) 1.

[0007] Many types of water soluble packages are known, includingpackages made from polyvinyl alcohol (hereinafter referred to as “PVOH”)film. A wide variety of different materials can be packaged in suchfilms, including liquid materials.

[0008] EP-A-518689 discloses a containerisation system for hazardousmaterials (for example pesticides) comprising a PVOH film enclosing acomposition comprising the hazardous material, water, an electrolyte andoptional other materials. The electrolyte is added to reduce thesolubility of the film to prevent its dissolution by the packagedcomposition.

[0009] WO9737903 discloses films for the encapsulation ofagro-chemicals. There is no suggestion of films designed to respond tosurfactant concentration.

[0010] EP-B-389513 discloses concentrated aqueous syrups (mainlyfoodstuffs but other materials such as detergents are mentioned) insidePVOH packages, the concentration of the syrup being effective to preventdissolution of the package by the packaged composition.

[0011] EP-A-700989 discloses a unit packaged detergent for dish washing,the package comprising a detergent composition wrapped in PVOH film,wherein the film protects the detergent from dissolution until the mainwash cycle of the dish washing machine.

[0012] WO-A-97/27743 discloses an agrochemical composition packaged in awater soluble sachet, which can be PVOH.

[0013] GB-A-2118961 discloses bath preparations packaged in PVOH film,while EP-B-347221 relates to water-soluble sachets of phytosanitarymaterials which are packaged in a secondary water-insoluble pack with ahumid environment being maintained between the two.

[0014] EP-A-593952 discloses a water soluble sachet of PVOH with twochambers and a treatment agent for washing inside each chamber.

[0015] EP-A-941939 relates to a water soluble package, which can bePVOH, containing a composition which, when dissolved, produces asolution of known composition.

[0016] GB-A-2305931 discloses a dissolvable laundry sachet andBE-9700361 relates to a water soluble unit-dosed cleaning agent,especially for cleaning hands.

[0017] DE-29801621 discloses a water soluble unit dose for dishwashingmachines.

[0018] EP-B-160254 relates to a washing additive comprising a mixture ofdetergent constituents in a PVOH bag. The detergent comprises nonionicsurfactant and a quaternary ammonium compound. U.S. Pat. No. 4,846,992discloses a double-packaged laundry detergent wherein the inner packageis water-soluble and can be PVOH.

[0019] EP-B-158464 relates to a detergent mull packaged in PVOH andDE-A-19521140 discloses a water soluble PVOH sachet containing adetergent composition.

[0020] FR-2601930 relates to a water soluble sachet containing anysubstance, particularly a pharmaceutical.

[0021] A variety of water soluble PVOH films are also known. Forexample, EP-B-157162 relates to a self-supporting film comprising a PVOHmatrix having rubbery microdomains dispersed therein.

[0022] WO-A-96/00251 relates to an amphipathic graft copolymercomprising a hydrophobic backbone with grafting sites to which aregrafted a hydrophilic polymer prepared from a hydrophilic monomercontaining stabilising pH independent ionic groups.

[0023] GB-B-2090603 relates to a water soluble film comprising a uniformmixture of partially hydrolysed polyvinyl acetate and polyacrylic acid.

[0024] WO-A-97/00282 relates to a water soluble film combining twopolymeric ingredients S and H where S is a soft acid-functional olefinicaddition copolymer having a Tg less than 20° C. and H is a hardacid-functional olefinic addition copolymer having a Tg less than 40° C.The ratio of S:H is from 90:10 to 65:35 and the acid functionalities areat least partially neutralised to render the film water soluble.

[0025] EP-B-79712 relates to a laundry additive for discharge to a washcontaining borate ions. The additive is enclosed within a film of PVOHwhich is plasticised and has as a solubiliser either a polyhydroxycompound (such as sorbitol) or an acid (such as polyacrylic acid).

[0026] EP-B-291198 relates to a water soluble film containing analkaline or borate-containing additive. The film is formed from acopolymer resin of vinyl alcohol having 0-10 mole % residual acetategroups and 1-6 mole % of a non-hydrolysable anionic comonomer.FR-2724388 discloses a water soluble bottle, flask or drum made fromPVOH which is plasticised with 13-20% of plasticiser (such as glycerol)and then moulded.

[0027] The specifications of International Patent ApplicationsWO-A-00/55044, WO-A-00/55045, WO-A-00/55046, WO-A-00/55068,WO-A-00/55069 and WO-A-00/55415 disclose water soluble packagescontaining a fluid substance (defined as a liquid, gel or paste) whichis a horizontal form-fill-seal (HFFS) envelope. These packages comprisea body wall portion having internal volume and which is preferablydome-shaped, formed from a first sheet, and a superposed base wallportion, formed from a second sheet, seded to the body wall portion.

[0028] A PVOH package containing a liquid laundry detergent compositioncomprising from about 10% to about 24% by weight of water (but 3.57% inthe sole example) is disclosed in U.S. Pat. No. 4,973,416.

[0029] EP0283180 discloses the preparation of very fast dissolving filmswith a high degree of hydrolysis.

[0030] WO-A1-97/19961 discloses fast solubility polymers, made from PVOHco-polymerized with carboxylate moieties, and have some degree oflactonization. These materials dissolve quickly in detergent solution.There is no reference or suggestion to control of solubility usingwashing surfactants.

[0031] EP0284334 relates to films comprising a blend of PVOH and alkylcelluloses with a metal salt, such as borate, to produce a triggeredpouch. The alkyl cellulose is present to respond to temperature suchthat at low rinse temperatures it is more soluble than at the highertemperatures associated with the wash cycle. The borate cross linkingprovides pH sensitivity. Furthermore, this document discloses thatanionic surfactants have very little effect on or even increase the rateof dissolution of the film.

[0032] GB2358382 relates to rigid blow molded components made from PVOH.

[0033] AT408548 concerns PVOH materials that contain builders for theimprovement of detergency during the wash cycle.

[0034] When formulating a liquid unit dose product of the kind wherein asubstantially non-aqueous formulation is encapsulated in a water solublefilm, probably the most difficult challenge is to preserve the physicalintegrity and stability of the film. One approach to this problem isdisclosed in WO-A1-01/79417, which involves substantially neutralising,or over-neutralising any acidic components in the liquid composition,especially any fatty acids and/or acid precursors of anionic surfactant.However, this approach is specific to encapsulation using awater-soluble film based on PVOH which includes comonomer units havingcarboxyl functionality.

[0035] Preservation of the integrity of films which contain fabricsoftening compositions for use in the rinse cycle is particularlychallenging since commercial softening compositions are generallyaqueous and tend to interact undesirably with water soluble packagingcausing a weakening of the film and potentially premature breakage, e.g.during storage.

[0036] One way of addressing this problem is disclosed in U.S. Pat. No.4,765,916 which involves providing a cross-linked polymeric watersoluble film, preferably a borate.

[0037] Where the package is to deliver a fabric softening composition,it is important that the contents are delivered primarily during therinse cycle.

[0038] In the case of so-called “top-loading” washing machines where thefabric conditioning product is typically dosed directly into the drum ofthe washing machine, this usually requires that the consumer to bepresent both at the beginning of the wash cycle and at the beginning ofthe rinse cycle to dose the wash and rinse products respectively.

[0039] Accordingly, it is desirable to be able to provide a productwhich can be dosed into the washing machine drum at the beginning of thewash cycle but does not disperse or release its contents until the rinsecycle.

[0040] One way of addressing this problem is set out in WO-A1-02/102956,where a water soluble package is provided which is soluble in responseto, for instance, the change in pH and/or ionic strength from the washliquor to the rinse liquor. However, the variety of machines and washconditions means that changes in pH and/or ionic strength can varyenormously. Therefore, it is also desirable to provide a water solublepackage which can be dosed into the wash cycle and which is triggered inthe rinse cycle by an alternative means.

[0041] WO-A-01/85892 discloses highly concentrated conditioners withPVOH film receptacles which are added to the rinse compartment of thedosing drawer. The receptacle enters the rinse bath when the rinse cyclestarts.

[0042] WO-A-00/51724 discloses the use of molecular sieves forcontrolled release of fabric treatment products.

[0043] WO-A-00/06688 relates to PVOH films which are modified with anamine group. The film releases its contents due to a change in pH duringthe laundry cycle.

[0044] DE-A-2749555 discloses a two fold laminate with a washing pouch,released during the rinse. However, an insoluble bag remains after thelaundry cycle is complete. Furthermore, the polymers discloses thereinare not hydrophobically modified.

OBJECTS OF THE INVENTION

[0045] The present invention seeks to address one or more of theabove-mentioned problems and to provide one or more of theabove-mentioned benefits.

[0046] The inventors have now found that a water soluble package can bechemically modified so that the rate at which it breaks down, e.g.dissolves, disperses or otherwise disintegrates, is dependent on theconcentration of washing detergent present in a liquor.

[0047] In particular, it has been found that by modifying the structureof a water soluble polymeric film, such as a PVOH film, with a modifyinggroup, e.g. with a specific acetal group, the film remains substantiallyintact in the presence of an anionic and/or nonionic detergent, e.g.during the wash cycle of a laundry operation, and disintegrates when theconcentration of the detergent reduces sufficiently, e.g. during therinse cycle of the laundry operation.

SUMMARY OF THE INVENTION

[0048] Thus, according to the present invention there a water solublepackage for use in the rinse cycle of a washing machine comprising apolymeric film, the polymeric film comprising a polymeric backbonederived from a polymer which is water soluble, as defined herein, andone or more derivatising groups attached to the backbone, thederivatising group(s) being derived from a material having a ClogP offrom 0.5 to 6.

[0049] According to another aspect of the invention, a water solublepackage comprises a polymeric film, the polymeric film comprising apolymeric backbone derived from a polymer which is water soluble, asdefined herein, and one or more derivatising groups attached to thebackbone, the derivatising group(s) being derived from a parent materialcomprising a C4 to C22 hydrocarbyl chain.

[0050] According to yet another aspect of the invention, a water solublepackage comprises a polymeric film, the polymeric film comprising apolymeric backbone derived from a polymer which is water soluble, asdefined herein, and one or more derivatising groups attached to thebackbone wherein the package has a relative rupture ratio of greaterthan 1, more preferably greater than 3 most preferably greater than 7.

[0051] Preferably, the water soluble package has a solubility ordispersibility in anionic or combinations of anionic/nonionicsurfactants of more than 15 minutes when the surfactant concentration inwater is greater than 0.05 g/L and a solubility or dispersibility ofless than 15 minutes when the surfactant concentration in water is lessthan 0.05 g/L.

[0052] Preferably the parent material from which the derivatising groupis obtained is an aldehyde.

[0053] It is particularly desirable that the polymeric film is capableof forming, upon contact with a detergent surfactant in a micellar orliquid crystalline form, a gelled network having a viscosity or anapparent molecular weight greater than the molecular weight of thepolymeric film alone.

[0054] In a further aspect, the invention provides a process forconditioning fabrics comprising the steps of adding to a laundry cycleof a washing machine the water soluble package as described herein andcontacting the contents of the package with fabric in the drum of thewashing machine.

[0055] In this process, it is preferred that the tendency of the watersoluble package to break down is reduced in the presence of a fabricwash detergent active.

DETAILED DESCRIPTION OF THE INVENTION

[0056] The water soluble package and any contents present therein mustbe compatible with each other. By “compatible” is meant that in an inertatmosphere free of moisture and at a temperature of from 5 to 40° C.,the water soluble package with the rinse conditioner contents thereindoes not rupture or release any contents within 4 weeks, more preferably8 weeks, most preferably 20 weeks.

[0057] Polymeric Film

[0058] The polymeric film used in the invention is a material whosedissolution/dispersion in a liquor is dependent upon the concentrationof any anionic and/or nonionic surfactant present in the liquor, suchthat the lower the concentration of anionic/nonionic surfactant in theliquor, the faster the film breaks down.

[0059] Without wishing to be bound by theory it is believed that thehydrophobic derivative within the polymeric film interacts with theanionic and/or non-ionic surfactants to form a gelled network during theduration of the wash cycle which renders the film substantiallyinsoluble, but which breaks down during the rinse cycle so that the filmbecomes substantially more soluble or dispersible.

[0060] In a practical application, the release of a rinse additive willoccur due to dissolution/dispersion as well as mechanical abrasion anderosion of the polymeric film. Dissolution/dispersion is influenced bythe molecular properties of the polymer such as its Flory-Hugginsinteraction parameter, whereas the mechanical properties of the polymerare related to its rheological behaviour under external stress orstrain.

[0061] Preferably the hydrophobically modified polymer has a solubilityor dispersibility at 20° C. in water which contains a concentration ofanionic/nonionic surfactant of greater than 1.3×10⁻⁴ mole/L of less than0.5 g per hour and a solubility or dispersibility of greater than 0.5 gper hour when the concentration of anionic/nonionic surfactant in wateris less than 1.3×10⁻⁴ mole/L.

[0062] According to one aspect of the invention, the package formed fromthe polymeric film has a relative rupture ratio of greater than 1, morepreferably greater than 3, most preferably greater than 7. As definedherein, the phrase “relative rupture ratio” means the ratio of the timetaken for a package to rupture in the presence of an anionic and/ornonionic surfactant relative to the time taken for the same package torupture in demineralised water.

[0063] According to another aspect of the invention, the derivatisinggroup attached to the backbone of the polymer is selected from a parentmaterial having a ClogP of from 0.5 to 6, more preferably from 1 to 6,most preferably from 2 to 6, e.g. 3 to 6.

[0064] In the context of the present invention, ClogP is calculatedaccording to the ClogP Calculator Version 4, available from DaylightChemicals Inc.

[0065] Preferred derivatising groups include those based on parentgroups selected from acetals, ketals, esters, fluorinated organiccompounds, ethers, alkanes, alkenes, aromatics. Especially preferredparent groups are aldehydes such as butyraldehyde, octyl aldehyde,dodecyl aldehyde, 2-ethyl hexanal, cyclohexane carboxy-aldehyde, citral,and 4-aminobutyraldehyde dimethyl acetal, although it will be readilyapparent to the person skilled in the art that other suitable parentgroups having the requisite ClogP are also suitable for use in thepolymeric film of the invention.

[0066] Additional modifying groups may be present on the polymerbackbone. For instance, amines may preferably be included as a modifyinggroup since this makes the polymer more soluble in response to, forinstance, the change in pH and/or ionic strength from the wash liquor tothe rinse liquor.

[0067] The derivatising group preferably comprises an optionallysubstituted hydrocarbyl chain.

[0068] According to another aspect of the invention, the hydrocarbylchain length of the derivatising group attached to the polymericbackbone is from 4 to 22, more preferably from 4 to 20, even morepreferably from 4 to 15, most preferably from 4 to 10, e.g. from 4 to 8.

[0069] Hydrocarbyl chain lengths shorter than 4 are undesirable as, inuse, the gel-like structure formed at the interface of the polymericfilm and any detergent surfactant will typically be too weak and willallow the package to rupture during the wash cycle rather than the rinsecycle.

[0070] Hydrocarbyl chain lengths greater than 22 are undesirable as theparent material from which the derivatising group is obtained reactspoorly or not at all with the polymeric backbone.

[0071] The hydrocarbyl chain length of the original function on theparent material from which the derivatising group is obtained ispreferably from 4 to 22, more preferably from 5 to 20.

[0072] In this context, the number of carbons in the hydrocarbyl groupincludes any carbon within the chain attached to any other functionalgroup within the derivatising material. For instance, butyraldehyde hasa hydrocarbyl chain length of 4.

[0073] The derivatising material is preferably present in the polymer ata level of from 0.1 to 40% by weight, based on the total weight of thepolymer, more preferably 2 to 30%, most preferably 5 to 15%, e.g. 8 to12%.

[0074] Where the polymeric backbone is based on PVOH, the derivatisingmaterial is preferably present at a level such that the number ratio ofthe derivative groups to the free hydroxyl pairs on the backbone is from1:3 to 1:30, more preferably 1:4 to 1:20, most preferably 1:7 to 1:15,e.g. 1:8 to 1:13.

[0075] Below a ratio of 1:30, the stability of the material during thewash phase is particularly weak and so a package may not survive intactuntil the rinse phase.

[0076] Above a ratio of 1:3, the resulting polymer may not fragmentand/or dissolve sufficiently. This can cause high residue after therinse phase, which is undesirable for consumers.

[0077] In the context of the present invention, “water soluble polymer”is defined as a material having a solubility in water at 20° C. of morethan 0.1 g/litre, preferably more than 0.3 g/litre, most preferably morethan 0.5 g/litre.

[0078] Preferred polymers from which the backbone of the derivatisedpolymeric film of the invention is formed include water-soluble resinssuch as PVOH, cellulose ethers, polyethylene oxide (hereinafter referredto as “PEO”), starch, polyvinylpyrrolidone (hereinafter referred to as“PVP”), polyacrylamide, polyvinyl methyl ether-maleic anhydride,polymaleic anhydride, styrene maleic anhydride, hydroxyethylcellulose,methylcellulose, polyethylene glycols, carboxymethylcellulose,polyacrylic acid salts, alginates, acrylamide copolymers, guar gum,casein, ethylene-maleic anhydride resin series, polyethyleneimine, ethylhydroxyethylcellulose, ethyl methylcellulose, hydroxyethylmethylcellulose. Water-soluble, PVOH film-forming resins areparticularly preferred.

[0079] Generally, preferred water-soluble, PVOH-based film-formingpolymers should have relatively low average molecular weight and highlevels of hydrolysis in water. Polyvinyl alcohol-based polymerspreferred for use herein have an average molecular weight of from 1,000to 300,000, preferably from 2,000 to 100,000, most preferably from 2,000to 75,000. Hydrolysis, or alcoholysis, is defined as the percentcompletion of the reaction where acetate groups on the resin aresubstituted with hydroxyl, —OH, groups. A hydrolysis range of from60-99% of PVOH-based film-forming resin is preferred, while a morepreferred range of hydrolysis is from about 88-99%. As used in thisapplication, the term “PVOH” includes polyvinyl acetate compounds withlevels of hydrolysis disclosed herein.

[0080] Preferred PVOH polymers preferably have an average degree ofsaponification within the range from 70 to 99%, and a viscosity as a 7%solution within the range 100 to 5000 mPa.s at ambient temperaturemeasured at a shear rate of 20 s⁻¹.

[0081] All of the above polymers include the aforementioned polymerclasses whether as single polymers or as copolymers formed of monomerunits or as copolymers formed of monomer units derived from thespecified class or as copolymers wherein those monomer units arecopolymerised with one or more comonomer units.

[0082] A particularly preferred polymer for use in the present inventionis represented by the formula:

[0083] wherein the average number ratio of z to x is within the range offrom 1:200 to 1:6, more preferably from 1:100 to 1:8, most preferablyfrom 1:50 to 1:12, e.g. 1:30 to 1:14, y is the residual acetateremaining from the hydrolysis of the parent compound, which ispreferably in the range of from 1-20%, more preferably 1-10%, mostpreferably 1-5% and R is an alkyl or alkenyl group having from 3 to 22carbon atoms. More preferably R is an alkyl group having from 3 to 6carbon atoms. Most preferably R is C₃H₇.

[0084] Cross-Linking

[0085] In order to provide a water soluble package which maintainsintegrity and structure during the wash cycle but which dissolves ordisperses fully in the rinse cycle, it has also been found advantageousfor the water soluble film to be provided as a cross-linked polymericstructure.

[0086] Particularly suitable cross-linking agents include formaldehyde;polyesters; epoxides, amidoamines, anhydrides, phenols; isocyanates;vinyl esters; urethanes; polyimides; arylics; bis(methacrylkoxypropyl)tetramethylsiloxane (styrenes, methylmethacrylates); n-diazopyruvates;phenyboronic acids; cis-platin; divinylbenzene; polyamides; dialdehydes;triallyl cyanurates; N-(-2-ethanesulfonylethyl)pyridinium halides;tetraalkyltitanates; mixtures of titanates and borates or zirconates;polyvalent ions of Cr, Zr, Ti; dialdehydes, diketones; alcohol complexesof organotitanates, zircoates and borates and copper (II) complexes.

[0087] Most preferred as the cross-linking agent is boric acid or itssalt form, e.g. sodium borate.

[0088] Levels of cross-linking agent are dictated primarily by thephysical parameters of the film layer, e.g. molecular weight, percenthydrolysis and thickness, and secondarily by the additive and washconditions. The level of cross-linking agent, if present, is from about0.05% to 9% by weight of the film, more preferably 1% to 6%, mostpreferably about 1.5% to 5% by weight. The upper range will, of course,result in more cross-linking and a slower rate of dissolution ordispersion of the film in the rinse cycle.

[0089] Functionally, it is believed that the cross-linking agent reducesthe solubility of the film polymer by increasing its effective molecularweight. While it is preferred to incorporate the cross-linking agentdirectly into the film polymer, it is also within the scope of theinvention to maintain the film in contact with the cross-linking agentduring the wash. This may be done by adding the cross-linking agent tothe wash solution, or by encasing it within the film polymer. If thecross-linking agent is added in this manner, somewhat higher levels areneeded to sufficiently cross-link the film polymer, and should rangefrom about 1-15% by weight.

[0090] For PVOH-based films, the preferred cross-linking agent is ametalloid oxide such as borate, tellurate, arsenate, and precursorsthereof. Other known cross-linkers include the vanadyl ion, titanium ionin the plus three valence state, or a permanganate ion (disclosed inpatent U.S. Pat. No. 3,518,242). Alternative cross-linkers are given inthe book: Polyvinylalcohol—Properties and applications, Chapter 9 by C.A. Finch (John Wiley & Sons, New York, 1973).

[0091] Plasticiser and/or Crystallinity Disruptor

[0092] The film preferably incorporates a plasticiser and/orcrystallinity disrupter.

[0093] It is to be understood that the term “plasticiser” and phrase“crystallinity disrupter” are interchangeable such that a reference toone is an implicit reference to the other.

[0094] The plasticiser influences the way the polymer chains react toexternal factors such as compression and extensional forces, temperatureand mechanical shock by controlling the way that the chainsdistort/realign as a consequences of these intrusions and theirpropensity to revert or recover to their former state. The key featureof plasticisers is that they are highly compatible with the film, andare normally hydrophilic in nature.

[0095] The plasticiser will depend on the nature of the film inquestion.

[0096] Generally, plasticisers suitable for use with PVOH-based filmshave —OH groups in common with the —CH2-CH(OH)—CH2-CH(OH)— polymer chainof the film polymer.

[0097] Their mode of functionality is to introduce short chain hydrogenbonding with the chain hydroxyl groups and this weakens adjacent chaininteractions which inhibits swelling of the aggregate polymer mass—thefirst stage of film dissolution.

[0098] Water itself is a suitable plasticiser for PVOH films but othercommon plasticisers include:

[0099] Polyhydroxy compounds, e.g. glycerol, trimethylolpropane,diethylene glycol, triethylene glycol, sorbitol, dipropylene glycol,polyethylene glycol; starches, e.g. starch ether, esterificated starch,oxidized starch and starches from potato, tapioca and wheat;cellulosics/carbohydrates, e.g. amylopectin, dextrincarboxymethylcelluose and pectin. Amines are particularly preferredplasticisers.

[0100] PVP films exhibit excellent adhesion to a wide variety ofsurfaces, including glass, metals, and plastics. Unmodified films ofpolyvinylpyrrolidone are hygroscopic in character. Drypolyvinylpyrrolidone film has a density of 1.25 g.cm ⁻³ and a refractiveindex of 1.53. Tackiness at higher humidities may be minimized byincorporating compatible, water-insensitive modifiers into thepolyvinylpyrrolidone film, such as 10% of anaryl-sulfonamide-formaldehyde resin.

[0101] Suitable plasticisers for PVP-based films may be chosen from oneor more of:

[0102] phosphates e.g. tris(2-ethylhexyl)phosphate, isopropyl diphenylphosphate, tributoxyethylphosphate; polyols e.g. glycerol, sorbitol,diethylene glycol diperlargonate, polyethylene glycoldi-2-ethylhexanoate, dibutyl tartrate; polyol esters e.g. hydroxycontaining polycaprolactones, hydroxy containing poly-L-lactide; lowerphthalates e.g. dimethyl phthalate, diethyl phthalate, dibutyl pthalate;and sulfonamides e.g. toluene sulfonamide, N-ethyltoluene sulfonamide.

[0103] Preferred water-soluble films may also be prepared frompolyethylene oxide (PEO) resins by standard moulding techniques such ascalendering, casting, extrusion, and other conventional techniques. Thepolyethylene oxide films may be clear or opaque, and are inherentlyflexible, tough, and resistant to most oils and greases. Thesepolyethylene oxide resin films provide better solubility than otherwater-soluble plastics without sacrificing strength or toughness. Theexcellent ability to lay flat, stiffness, and sealability ofwater-soluble polyethylene oxide films make for good machine handlingcharacteristics.

[0104] Suitable plasticisers for PEO-based films may be selected fromone or more of:

[0105] phosphates e.g. tris(2-ethylhexyl)phosphate, isopropyl diphenylphosphate, tributoxyethylphosphate; polyols e.g. glycerol, sorbitol,diethylene glycol diperlargonate, polyethylene glycoldi-2-ethylhexanoate, dibutyl tartrate; lower phthalates e.g. dimethylphthalate, diethyl phthalate, dibutyl pthalate; and sulphonamides e.g.toluene sulphonamide, N-ethyltoluene sulphonamide.

[0106] If the plasticiser is present in the fabric conditioningcomposition, then the preferred amount of plasticiser is from 0.001% to25%, preferably from 0.005% to 4% by weight of the composition. One ormore plasticisers may independently be incorporated in the film and inthe liquid composition. However, it is very much preferred for theidentity of the plasticiser(s) in the film and in the liquid compositionto be substantially the same.

[0107] The plasticiser and/or crystallinity disruptor can be physicallybound to the backbone of the polymeric material as, for instance, whenthe plasticiser is provided as part of the fabric conditioningcomposition and/or can be chemically bound to the backbone of thepolymeric material, e.g. it can be covalently bound within the backboneof the polymeric film as described. A suitable method of chemicallybonding the plasticiser to the backbone of the polymeric material isdescribed in DE 10229213.2.

[0108] Protective Barrier

[0109] A protective material which provides a barrier between the filmand its contents may be present in the package. Such a barrier enables amore aqueous composition, which would typically cause a package todisintegrate rapidly, to be stored within the package without causingundesirable premature release of the contents.

[0110] A particularly suitable protective barrier material is PTFE, asdisclosed in U.S. Pat. No. 4,416,791.

[0111] It is also envisaged that the polymeric film can be furtherprotected from premature disintegration by a providing a coating ofanionic surfactant on the film. For instance, the film may be dustedwith anionic surfactant or a powdered detergent blend or the film may becast in the presence of an anionic surfactant.

[0112] Film Formation

[0113] Film forming on a laboratory scale can be conducted by adding anaqueous solution of the polymer, containing any plasticizers etc. to aPTFE bed, and allowing the film to form over 1 to 5 days. The resultingfilm thickness is nominally between 50 to 200 microns (dependent uponconcentration of polymer solution, and the surface area of the PTFE bed.

[0114] The aqueous polymer solution can be cast to a controlledthickness on a commercial scale using conventional methods andtechniques known in the art such as solution casting and thermo-formingtechniques.

[0115] Typically, in solution casting, the aqueous polymer solutions arecast on a plate or belt using a film applicator where they are allowedto dry. The films can then be vacuum dried, air dried etc. followed byremoval from the belt/plate. Casting techniques are described in U.S.Pat. No. 5,272,191 issued Dec. 21, 1993, to Ibrahim et. al. which isincorporated herein for reference.

[0116] Films can also be prepared using a melt process, which typicallyinvolves mixing the polymer with sufficient water to melt below itsdecomposition temperature. The blended polymer and water matrix is thenfed to an extruder, extruded under tension through an appropriate die,cooled with air and taken up by an appropriate collection device. Formaking films, a tubular film can be made by blowing cool air through thecentre of the tube to cool the film and to impart a biaxial stress tothe film. Extrusion processes can also be used to make other shapedarticles by using appropriate dies and moulds. Examples of such thermoforming processes are described in more detail in U.S. Pat. No.5,646,206 issued Jul. 8, 1997, to Coffin et Al. incorporated herein byreference.

[0117] Water Soluble Package

[0118] Preferably the package comprising the film is a “delayed release”package. “Delayed Release” is defined herein as a package which, whenplaced in the drum at the beginning of the wash cycle, remainssubstantially intact during the wash cycle and then disperses ordissolves at the beginning of or during the rinse cycle.

[0119] In addition to the modification of the film so that itssolubility is dependent upon detergent concentration in the wash liquor,a trigger source, which activates or accelerates dispersal ordissolution of the water soluble package once the rinse cycle commencesmay also desirably be present.

[0120] Suitable trigger sources include, for instance, those describedin WO-A1-02/102956 such as sources/materials for causing changes in pH,temperature, electrolytic conditions, light, time or molecularstructure. Such triggers may be used alone or in combination with eachother.

[0121] The rinse conditioner formulation itself may also be designed soas to aid and/or control the dissolution or and/or dispersion of thepackage.

[0122] It is particularly preferred that, at wash levels of detergent,having an anionic loading of 0.05 g/L to 2 g/L (based on LAS with anaverage molecular weight of 242), the package remains intact for greaterthan 15 minutes and, at rinse levels of detergent the package breaksdown and disperses within 15 minutes, more preferably within 7 minutes.

[0123] The film for the package preferably has an average thickness offrom 50 to 500 μm, more preferably from 60 to 300 μm, most preferablyfrom 65 to 250 μm.

[0124] Typically the water soluble package will be in the form of apouch for containing a distinct fabric treatment composition.Alternatively, or additionally, the package may comprise a network ormatrix of the film and fabric treatment composition where there isphysical and/or chemical interaction between the film and treatmentcomposition.

[0125] Encapsulation Methods

[0126] Any reference herein to filling refers to complete filling andalso partial filling whereby some air or other gas is also trapped inthe sealed envelope.

[0127] The envelope forming the package is preferably formed byhorizontal or vertical form-film-seal technique.

[0128] (a) Horizontal Form-Fill-Seal

[0129] Water soluble packages based on derivatised PVOH can be madeaccording to any of the horizontal form-fill-seal methods described inany of WO-A-00/55044, WO-A-00/55045, WO-A-00/55046, WO-A-00/55068,WO-A-00/55069 and WO-A-00/55415.

[0130] By way of example, a thermoforming process is now described wherea number of packages according to the invention are produced from twosheets of water soluble material. In this regard recesses are formed inthe film sheet using a forming die having a plurality of cavities withdimensions corresponding generally to the dimensions of the packages tobe produced. Further, a single heating plate is used for thermoformingthe film for all the cavities, and in the same way a single sealingplate is described.

[0131] A first sheet of derivatised PVOH film is drawn over a formingdie so that the film is placed over the plurality of forming cavities inthe die. In this example each cavity is generally dome shape having around edge, the edges of the cavities further being radiussed to removeany sharp edges which might damage the film during the forming orsealing steps of the process. Each cavity further includes a raisedsurrounding flange. In order to maximise package strength; the film isdelivered to the forming die in a crease free form and with minimumtension. In the forming step, the film is heated to 100 to 120° C.,preferably approximately 110° C., for up to 5 seconds, preferablyapproximately 700 micro seconds. A heating plate is used to heat thefilm, which plate is positioned to superpose the forming die. Duringthis preheating step, a vacuum of 50 kPa is pulled through thepre-heating plate to ensure intimate contact between the film and thepre-heating plate, this intimate contact ensuring that the film isheated evenly and uniformly (the extent of the vacuum is dependant ofthe thermoforming conditions and the type of film used, however in thepresent context a vacuum of less than 0.6 kPa was found to be suitable).Non-uniform heating results in a formed package having weak spots. Inaddition to the vacuum, it is possible to blow air against the film toforce it into intimate contact with the preheating plate.

[0132] The thermoformed film is moulded into the cavities blowing thefilm off the heating plate and/or by sucking the film into the cavitiesthus forming a plurality of recesses in the film which, once formed, areretained in their thermoformed orientation by the application of avacuum through the walls of the cavities. This vacuum is maintained atleast until the packages are sealed. Once the recesses are formed andheld in position by the vacuum, a liquid composition according to theinvention is added to each of the recesses. A second sheet of polyvinylalcohol film is then superposed on the first sheet across the filledrecesses and heat-sealed thereto using a sealing plate. In this case theheat sealing plate, which is generally flat, operates at a temperatureof about 140 to 160° C., and contacts the films for 1 to 2 seconds andwith a force of 8 to 30 kg/cm², preferably 10 to 20 kg/cm². The raisedflanges surrounding each cavity ensure that the films are sealedtogether along the flange to form a continuous seal. The radiussed edgeof each cavity is at least partly formed by a resiliently deformablematerial, such as for example silicone rubber. This results in reducedforce being applied at the inner edge of the sealing flange to avoidheat/pressure damage to the film.

[0133] Once sealed, the packages formed are separated from the web ofsheet film using cutting means. At this stage it is possible to releasethe vacuum on the die, and eject the formed packages from the formingdie. In this way the packages are formed, filled and sealed whilenesting in the forming die. In addition they may be cut while in theforming die as well.

[0134] During the forming, filling and sealing steps of the process, therelative humidity of the atmosphere is controlled to ca. 50% humidity.This is done to maintain the heat sealing characteristics of the film.When handling thinner films, it may be necessary to reduce the relativehumidity to ensure that the films have a relatively low degree ofplasticisation and are therefore stiffer and easier to handle.

[0135] (b) Vertical Form-Fill-Seal

[0136] In the vertical form-fill-seal (VFFS) technique, a continuoustube of flexible plastics film is extruded. It is sealed, preferably byheat or ultrasonic sealing, at the bottom, filled with the liquidcomposition, sealed again above the liquid film and then removed fromthe continuous tube, e.g. by cutting.

[0137] Unit Dose Volume

[0138] The amount of the product, preferably liquid product, morepreferably substantially non-aqueous liquid product, in each package ispreferably from 0.5 ml to 100 ml, more preferably from 1 ml to 30 ml,most preferably from 1.5 ml to 25 ml, e.g. from 2 ml to 15 ml.

[0139] Rinse Conditioning Composition

[0140] The water soluble package is constructed so as to be able toreceive a fabric treatment composition. A particularly preferredtreatment composition is a rinse conditioning composition, e.g. a fabricsoftening composition.

[0141] It is preferable that the rinse conditioning composition issubstantially non-aqueous so as to be compatible with the immediaterelease water soluble polymeric film.

[0142] It is desirable that the rinse conditioner can dissolve and/ordisperse rapidly once it is released from the package.

[0143] In the context of the present invention, “rapidly” in relation todispersal and/or dissolution of the rinse conditioner composition meanswithin 20 minutes, more preferably less than 15 minutes, most preferablyless than 12 minutes, e.g. less than 10 minutes in water at 25° C. orless.

[0144] In the context of the present invention, “substantiallynon-aqueous” means that the level of water or other aqueous componentsin the rinse conditioner composition is less than 20% by weight of thetotal weight of the rinse conditioner composition, more preferably 15%or less by weight, most preferably 10%, e.g. 5% or even 3% or less byweight.

[0145] Compositions which are compatible with the water soluble film andwhich dissolve and/or disperse rapidly in cold water include thefollowing:

[0146] Substantially non-aqueous concentrated melts, concentratedemulsions and microemulsions.

[0147] For the purposes of the present invention, a substantiallynon-aqueous concentrated melts is defined as a fabric conditioningcomposition present in solid form, such as particles, at a specifiedtemperature, the solid being suspended in an oil matrix and containingless than 20 wt %, preferably less than 5 wt % of water.

[0148] A substantially non-aqueous concentrated rinse conditioneremulsion is defined as a mixture of a quaternary ammonium softeningmaterial, an oil and water comprising more than 10 wt % of thequaternary ammonium material and less than 20 wt % of water.

[0149] A substantially non-aqueous microemulsion is defined as acomposition comprising less than 20% by weight water, wherein thecomposition is clear, isotropic and thermodynamically stable across arange of temperatures.

[0150] The following conventional ingredients are optionally present inthe compositions compatible with the packages used in the invention.

[0151] Cationic Fabric Softening Compound

[0152] The fabric softening compound is selected from those typicallyincluded in rinse-added fabric softening compositions.

[0153] It is especially preferred if the cationic softening agent is awater insoluble quaternary ammonium material which comprises a compoundhaving two C₁₂₋₁₈ alkyl or alkenyl groups connected to the nitrogen headgroup via at least one ester link. It is more preferred if thequaternary ammonium material has two ester links.

[0154] The first group of cationic fabric softening compounds for use inthe invention is represented by formula (I):

[0155] wherein each R is independently selected from a C₅₋₃₅ alkyl oralkenyl group, R¹ represents a C₁₋₄ alkyl, C₂₋₄ alkenyl or a C₁₋₄hydroxyalkyl group,

[0156] T is

[0157] n is 0 or a number selected from 1 to 4, m is 1, 2 or 3 anddenotes the number of moieties to which it relates that pend directlyfrom the N atom, and X⁻ is an anionic group, such as halides or alkylsulphates, e.g. chloride, methyl sulphate or ethyl sulphate.

[0158] Especially preferred materials within this class are di-alkenylesters of triethanol ammonium methyl sulphate. Commercial examplesinclude Tetranyl AHT-1 (di-hardened oleic ester of triethanol ammoniummethyl sulphate 80% active), AT-1(di-oleic ester of triethanol ammoniummethyl sulphate 90% active), L5/90 (palm ester of triethanol ammoniummethyl sulphate 90% active), all ex Kao, and Rewoquat WE15 (C₁₀-C₂₀ andC₁₆-C₁₈ unsaturated fatty acid reaction products with triethanolaminedimethyl sulphate quaternised 90% active), ex Witco Corporation.

[0159] The second group of cationic fabric softening compounds for usein the invention is represented by formula (II):

[0160] wherein each R group is independently selected from C₁₋₄ alkyl,hydroxyalkyl or C₂₋₄ alkenyl groups; and wherein each R² group isindependently selected from C₈₋₂₈ alkyl or alkenyl groups; n is 0 or aninteger from 1 to 5 and T and X are as defined above.

[0161] Preferred materials of this class such as1,2bis[tallowoyloxy]-3-trimethylammonium propane chloride and1,2-bis[oleyloxy]-3-trimethylammonium propane chloride and their methodof preparation are, for example, described in U.S. Pat. No. 4,137,180(Lever Brothers), the contents of which are incorporated herein.

[0162] A third group of cationic fabric softening compounds for use inthe invention is represented by formula (III):

[0163] wherein each R¹ group is independently selected from C₁₋₄ alkyl,or C₂₋₄ alkenyl groups; and wherein each R group is independentlyselected from C₈₋₂₈ alkyl or alkenyl groups; n is 0 or an integer from 1to 5 and T and X⁻ are as defined above. A preferred material within thisclass is N,N-di(tallowoyloxyethyl)-N,N-dimethyl ammonium chloride.

[0164] A fourth group of cationic fabric softening compounds for use inthe invention is represented by formula (IV):

[0165] wherein each R¹ group is independently selected from C₁₋₄ alkyl,or C₂₋₄ alkenyl groups; and wherein each R² group is independentlyselected from C₈₋₂₈ alkyl or alkenyl groups; and X⁻ is as defined above.

[0166] Preferably, the compositions are provided as superconcentratescomprising from 25-97% by weight of cationic surfactant (activeingredient) based on the total weight of the composition, morepreferably 35-95% by weight, most preferably 45-90% by weight, e.g.55-85% by weight.

[0167] If the quaternary ammonium softening agent comprises hydrocarbylchains formed from fatty acids or fatty acyl compounds which areunsaturated or at least partially unsaturated (e.g. having an iodinevalue of from 5 to 140, preferably 5 to 100, more preferably 5 to 60,most preferably 5 to 40, e.g. 5 to 25), then the cis:trans isomer weightratio of the chains in the fatty acid/fatty acyl compound is greaterthan 20:80, preferably greater than 30:70, more preferably greater than40:60, most preferably greater than 50:50, e.g. 70:30 or greater. It isbelieved that higher cis:trans isomer weight ratios afford thecompositions comprising the compound better low temperature stabilityand minimal odour formation. Suitable fatty acids include Radiacid 406,ex. Fina.

[0168] Saturated and unsaturated fatty acids/acyl compounds may be mixedtogether in varying amounts to provide a compound having the desirediodine value.

[0169] Fatty acids/acyl compounds may also be, at least partiallyhydrogenated to achieve lower iodine values.

[0170] Of course, the cis:trans isomer weight ratios can be controlledduring hydrogenation by methods known in the art such as by optimalmixing, using specific catalysts and providing high H₂ availability.

[0171] For improved rapid dispersion and/or dissolution of thecomposition after its release from the water soluble package, it ispreferred that the fatty acyl compounds or fatty acids from which thesoftening compound is formed have an average iodine value of from 5 to140, more preferably 10 to 100, most preferably 15 to 80, e.g. 25 to 60.

[0172] Iodine Value of the Parent Fatty Acid

[0173] The method for calculating the iodine value of a parent fattyacyl compound/acid is

[0174] The method for calculating the iodine value is as described inWO-A1-01/04254.

[0175] Oily Sugar Derivatives

[0176] Oily sugar derivatives may also be present in the composition.The oily sugar derivative is preferably present in an amount of from0.001 to 10 wt %, more preferably 0.01 to 5 wt %, most preferably 0.1 to4 wt % based on the total weight of the composition. Preferred oilysugar derivatives are those described as CPE's or RSE's inWO-A-96/16538. A particularly preferred oily sugar derivative is apolyester of sucrose.

[0177] Formulation and Dispersion Aids

[0178] Suitable formulation and/or dispersion aids for use in thecomposition are preferably substantially non-aqueous. Examples includeone or more of the following components:

[0179] (a) nonionic stabilising agents;

[0180] (b) polymeric stabilisers;

[0181] (c) single chain cationic surfactants;

[0182] (d) fatty alcohols or acids;

[0183] (e) short chain alcohols or oils; or

[0184] (f) electrolytes

[0185] Nonionic Stabilising Agents

[0186] Suitable nonionic stabilising agents are nonionic surfactants.

[0187] Preferred nonionic surfactants include addition products ofethylene oxide and/or propylene oxide with fatty alcohols, fatty acidsand fatty amines.

[0188] Any of the alkoxylated materials of the particular type describedhereinafter can be used as the nonionic surfactant.

[0189] Suitable surfactants are substantially water soluble surfactantsof the general formula:

R—Y—(C₂H₄O)_(z)—C₂H₄OH

[0190] where R is selected from the group consisting of primary,secondary and branched chain alkyl and/or acyl hydrocarbyl groups;primary, secondary and branched chain alkenyl hydrocarbyl groups; andprimary, secondary and branched chain alkenyl-substituted phenolichydrocarbyl groups; the hydrocarbyl groups having a chain length of from8 to about 25, preferably 10 to 20, e.g. 14 to 18 carbon atoms.

[0191] In the general formula for the alkoxylated nonionic surfactant, Yis typically:

—O—, —C(O)O—, —C(O)N(R)— or —C(O)N(R)R—

[0192] in which R has the meaning given above or can be hydrogen; and Zis preferably from 8 to 40, more preferably from 10 to 30, mostpreferably from 11 to 25, e.g. 12 to 22.

[0193] The level of alkoxylation, Z, denotes the average number ofalkoxy groups per molecule.

[0194] Preferably the nonionic surfactant has an HLB of from about 7 toabout 20, more preferably from 10 to 18, e.g. 12 to 16.

[0195] Examples of nonionic surfactants follow. In the examples, theinteger defines the number of ethoxy (EO) groups in the molecule.

[0196] A. Straight-Chain, Primary Alcohol Alkoxylates

[0197] The deca-, undeca-, dodeca-, tetradeca-, and pentadecaethoxylatesof n-hexadecanol, and n-octadecanol having an HLB within the rangerecited herein are useful viscosity/dispersibility modifiers in thecontext of this invention. Exemplary ethoxylated primary alcohols usefulherein as the viscosity/dispersibility modifiers of the compositions areC₁₈ EO(10); and C₁₈ EO(11). The ethoxylates of mixed natural orsynthetic alcohols in the “tallow” chain length range are also usefulherein. Specific examples of such materials include tallowalcohol-EO(11), tallow alcohol-EO(18), and tallow alcohol-EO (25), cocoalcohol-EO(10), coco alcohol-EO(15), coco alcohol-EO(20) and cocoalcohol-EO(25).

[0198] B. Straight-Chain, Secondary Alcohol Alkoxylates

[0199] The deca-, undeca-, dodeca-, tetradeca-, pentadeca-, octadeca-,and nonadeca-ethoxylates of 3-hexadecanol, 2-octadecanol, 4-eicosanol,and 5-eicosanol having an HLB within the range recited herein are usefulviscosity and/or dispersibility modifiers in the context of thisinvention. Exemplary ethoxylated secondary alcohols useful herein as theviscosity and/or dispersibility modifiers of the compositions are: C16EO(11); C₂₀ EO(11); and C₁₆ EO(14).

[0200] C. Alkyl Phenol Alkoxylates

[0201] As in the case of the alcohol alkoxylates, the hexa- tooctadeca-ethoxylates of alkylated phenols, particularly monohydricalkylphenols, having an HLB within the range recited herein are usefulas the viscosity and/or dispersibility modifiers of the instantcompositions. The hexa- to octadeca-ethoxylates of p-tri-decylphenol,m-pentadecylphenol, and the like, are useful herein. Exemplaryethoxylated alkylphenols useful as the viscosity and/or dispersibilitymodifiers of the mixtures herein are: p-tridecylphenol EO(11) andp-pentadecylphenol EO(18).

[0202] As used herein and as generally recognized in the art, aphenylene group in the nonionic formula is the equivalent of an alkylenegroup containing from 2 to 4 carbon atoms. For present purposes,nonionics containing a phenylene group are considered to contain anequivalent number of carbon atoms calculated as the sum of the carbonatoms in the alkyl group plus about 3.3 carbon atoms for each phenylenegroup.

[0203] D. Olefinic Alkoxylates

[0204] The alkenyl alcohols, both primary and secondary, and alkenylphenols corresponding to those disclosed immediately hereinabove can beethoxylated to an HLB within the range recited herein and used as theviscosity and/or dispersibility modifiers of the instant compositions.

[0205] E. Branched Chain Alkoxylates

[0206] Branched chain primary and secondary alcohols which are availablefrom the well-known “OXO” process can be ethoxylated and employed as theviscosity and/or dispersibility modifiers of compositions herein.

[0207] F. Polyol Based Surfactants

[0208] Suitable polyol based surfactants include sucrose esters suchsucrose monooleates, alkyl polyglucosides such as stearyl monoglucosidesand stearyl triglucoside and alkyl polyglycerols.

[0209] The above nonionic surfactants are useful in the presentcompositions alone or in combination, and the term “nonionic surfactant”encompasses mixed nonionic surface active agents.

[0210] The nonionic surfactant is present in an amount from 0.01 to 10%,more preferably 0.1 to 5%, most preferably 0.35 to 3.5%, e.g. 0.5 to 2%by weight, based on the total weight of the composition.

[0211] Polymeric Stabilisers

[0212] Polymeric stabilisers suitable for use in the compositionspreferably comprise at least 2% by weight of water soluble groups eitherwithin the main polymer backbone or pendant thereto.

[0213] Examples of suitable polymeric materials within this classinclude PVA; polylactones such as polycaprolactone and polylactide;methyl cellulose; derivativised starches; derivatives of cellulose; andcationic polymers such as Guar Gum.

[0214] If present, it is desirable to incorporate such polymers at alevel of from 0.01 to 5%, more preferable 0.05 to 3.5%, most preferablyfrom 1 to 2% by weight of the polymer based on the total weight of thecomposition.

[0215] Single Chain Cationic Surfactants

[0216] The compositions of the invention optionally contain a singlechain cationic surfactant.

[0217] The single chain cationic surfactant are particularly suitablefor use in emulsions since they can be employed in the formulation toaid the dispersion characteristics of the emulsion and/or to emulsifythe composition, in order to form a macroemulsion having oil dropletswhich are smaller than those in macroemulsion compositions comprisingthe cationic fabric softening agent alone.

[0218] The single chain cationic surfactant is preferably a quaternaryammonium compound comprising a hydrocarbyl chain having 8 to 40 carbonatom, more preferably 8 to 30, most preferably 12 to 25 carbon atoms(e.g. quaternary ammonium compounds comprising a C₁₀₋₁₈ hydrocarbylchain are especially preferred).

[0219] Examples of commercially available single chain cationicsurfactants which may be used in the compositions of the inventioninclude; ETHOQUAD (RTM) 0/12 (oleylbis(2-hydroxyethyl)methylammoniumchloride); ETHOQUAD (RTM) C12 (cocobis(2-hydroxyethyl)methyl ammoniumchloride) and ETHOQUAD (RTM) C25 polyoxyethylene(15)cocomethylammoniumchloride), all ex. Akzo Nobel; SERVAMINE KAC (RTM),(cocotrimethylammonium methosulphate), ex. Condea; REWOQUAT (RTM) CPEM,(coconutalkylpentaethoxymethylammonium methosulphate), ex. Witco;cetyltrimethylammonium chloride (25% solution supplied by Aldrich);RADIAQUAT (RTM) 6460, (coconut oil trimethylammonium chloride), ex. FinaChemicals; NORAMIUM (RTM) MC50, (oleyltrimethylammonium chloride), ex.Elf Atochem.

[0220] The single chain cationic surfactant is preferably present in anamount from 0 to 5% by weight, more preferably 0.01 to 3% by weight,most preferably 0.5 to 2.5% by weight, based on the total weight of thecomposition.

[0221] Fatty Alcohols, Acids or Oils

[0222] The formulation aid may further be selected from fatty alcohols,acids or oils, for example C₈ to C₂₄ alkyl or alkenyl monocarboxylicacids, alcohols or polymers thereof and C₈ to C₃₅ oils. Preferablysaturated fatty acids or alcohols are used, in particular, hardenedtallow C₁₆ to C₁₈ fatty acids.

[0223] Preferably the fatty acid is non-saponified, more preferably thefatty acid is free, for example oleic acid, lauric acid or tallow fattyacid. The level of fatty acid material is preferably more than 0.1% byweight, more preferably more than 0.2% by weight. Concentrated andsuperconcentrated compositions may comprise from 0.5 to 20% by weight offatty acid, more preferably 1% to 10% by weight.

[0224] Suitable fatty acids include stearic acid (PRIFAC 2980), myristicacid (PRIFAC 2940), lauric acid (PRIFAC 2920), palmitic acid (PRIFAC2960), erucic acid (PRIFAC 2990), sunflower fatty acid (PRIFAC 7960),tallow acid (PRIFAC 7920), soybean fatty acid (PRIFAC 7951) all ex.Uniqema; azelaic acid (EMEROX 1110) ex. Henkel.

[0225] The fatty acid may also act as a co-softener in the rinseconditioner composition.

[0226] The formulation aid may comprise a long chain oil. The oil may bea mineral oil, an ester oil, a silicone oil and/or natural oils such asvegetable or essential oils. However, ester oils or mineral oils arepreferred.

[0227] The ester oils are preferably hydrophobic in nature. They includefatty esters of mono or polyhydric alcohols having from 1 to 24 carbonatoms in the hydrocarbon chain, and mono or polycarboxylic acids havingfrom 1 to 24 carbon atoms in the hydrocarbon chain, provided that thetotal number of carbon atoms in the ester oil is equal to or greaterthan 8, and that at least one of the hydrocarbon chains has 12 or morecarbon atoms.

[0228] Suitable ester oils include saturated ester oils, such as thePRIOLUBES (ex. Uniqema). 2-ethyl hexyl stearate (PRIOLUBE 1545),neopentyl glycol monomerate (PRIOLUBE 2045) and methyl laurate (PRIOLUBE1415) are particularly preferred although oleic monoglyceride (PRIOLUBE1407) and neopentyl glycol dioleate (PRIOLUBE 1446) are also suitable.

[0229] It is preferred that the viscosity of the ester oil is from 0.002to 0.4 Pa.S (2 to 400 cps) at a temperature of 25° C. at 106 s⁻¹,measured using a Haake rotoviscometer NV1, and that the density of themineral oil is from 0.8 to 0.9 g.cm⁻³ at 25° C.

[0230] Suitable mineral oils include branched or straight chainhydrocarbons (e.g. paraffins) having 8 to 35, more preferably 9 to 20carbon atoms in the hydrocarbon chain.

[0231] Preferred mineral oils include the Marcol technical range of oils(ex. Esso) although particularly preferred is the Sirius range (ex.Silkolene) or Semtol (ex. Witco Corp.). The molecular weight of themineral oil is typically within the range 100 to 400.

[0232] One or more oils of any of the above mentioned types may be used.

[0233] It is believed that the oil provides excellent perfume deliveryto the cloth and also increases perfume longevity upon storage of thecomposition.

[0234] The oil may be present in an amount from 0.1 to 40% by weight,more preferably 0.2-20%, by weight, most preferably 0.5-15% by weightbased on the total weight of the composition.

[0235] Short Chain Alcohols

[0236] The formulation aid may comprise a short chain alcohol. Preferredare low molecular weight alcohols having a molecular weight ofpreferably 180 or less. The alcohol may be mono or polyhydric.

[0237] The presence of the lower molecular weight alcohol helps improvephysical stability upon storage by lowering the viscosity to a moredesired level and also assists the formation of the micro-emulsion.Examples of suitable alcohols include ethanol, isopropanol, n-propanol,dipropylene glycol, t-butyl alcohol, hexylene glycol, and glycerol.

[0238] The alcohol is preferably present in an amount from 0.1% to 40%by weight, more preferably from 0.2% to 35%, most preferably 0.5 to 20%by weight based on the total weight of the composition.

[0239] Electrolytes

[0240] The fabric softening composition optionally comprises anelectrolyte.

[0241] The electrolyte may be an inorganic or organic electrolyte.

[0242] Preferably the electrolyte is present in an amount from 0.001 to1.5%, more preferably 0.01 to 1%, most preferably 0.02 to 0.7% by weightbased on the total weight of the composition.

[0243] Suitable inorganic electrolytes include sodium sulphate, sodiumchloride, calcium(II) chloride, magnesium(II) chloride, potassiumsulphate and potassium chloride.

[0244] Suitable organic electrolytes include sodium acetate, potassiumacetate, sodium citrate, potassium citrate and sodium benzoate.

[0245] The electrolyte improves viscosity control (especially viscosityreduction) of the compositions and assists dispersion of thecomposition.

[0246] Co-Active Softening Surfactants

[0247] Co-active softening surfactants for the cationic surfactant mayalso be incorporated in an amount from 0.01 to 20% by weight, morepreferably 0.05 to 10%, based on the total weight of the composition.Preferred co-active softening surfactants are fatty amines and fattyN-oxides.

[0248] Perfume

[0249] The perfume may be any perfume conventionally used in fabricsoftening compositions. The perfume will thus preferably be compatiblewith the types fabric softening actives typically found in fabricsoftening compositions, although, not many commercially availableperfumes will not be compatible. Also the perfume will generally bepolar in nature.

[0250] The perfume used in the invention may be lipophilic in nature. Bya lipophilic perfume is meant that the perfume has a solubility in water(i.e. it dissolves) of 1 g or less in 100 ml of water at 20° C.Preferably solubility in water is 0.5 g or less, preferably 0.3 g orless. Such perfumes may be referred to as water-insoluble perfumes.

[0251] Perfumes contain a number of ingredients which may be naturalproducts or extracts such as essential oils, absolutes, resinoids,resins etc. and synthetic perfume components such as hydrocarbons,alcohols, aldehydes, ketones ethers, acids, esters, acetals, ketals,nitrites, phenols, etc. including saturated and unsaturated compounds,aliphatic, alicyclic, heterocyclic and aromatic compounds. Examples ofsuch perfume components are to be found in “Perfume and FlavourChemicals” by Steffen Arctander (Library of Congress catalogue card no.75-91398).

[0252] When present, the perfume is used in a concentration ofpreferably from 0.01-20% by weight, more preferably from 0.05-17% byweight, most preferably from 1-10% by weight, e.g. 2 to 6% by weightbased on the total weight of the composition.

[0253] Other Optional Ingredients

[0254] The compositions may also contain one or more optionalingredients conventionally included in fabric conditioning compositionssuch as pH buffering agents, perfume carriers, fluorescers, colourants,hydrotropes, antifoaming agents, antiredeposition agents,polyelectrolytes, enzymes, optical brightening agents, pearlescers,anti-shrinking agents, anti-wrinkle agents, anti-spotting agents,germicides, fungicides, anti-corrosion agents, drape imparting agents,anti-static agents, ironing aids crystal growth inhibitors,anti-oxidants, anti-reducing agents and dyes.

[0255] The fabric treatment composition is substantially, and preferablyentirely, free of anionic detergent surfactants conventionally used asan active cleaning ingredient in a main wash detergent product.

[0256] Non-limiting examples of fully formulated compositions suitablefor use in the packages of the present invention are as follows:Composition 1 2 Quat^(a) 93-99 — Quat^(b) — 22.8 Sirius M85^(c) — 39.2ER 290^(d) — 15 Hexylene Glycol — 10 Tergitol 15-S-7^(e) — 6 Perfume 1-44 Water 0-5 3

[0257] Composition 3 4 5 6 Quat^(a) 35 35 35 35 Perfume  3  3  3  3Estol 1545^(b) 27 27 27 27 Estasol^(c) 10 NMP^(d) 10 DMSO^(e) 10 Benzylalcohol 10 Coco-3^(f)  5  5  5  5

[0258] The compositions were prepared by heating the ingredients understirring to 80° C. until clear, and then leaving to cool to ambienttemperature under low shear mixing, to form soft-solid pastes, or gels.

[0259] It will be readily apparent to the person skilled in the art thatthe compositions hereinabove as merely examples and many morecompositions will be compatible with the polymeric film.

[0260] For instance, a suitable melt can be prepared by heating areaction vessel to at least 50° C., adding an oil and a nonionicsurfactant to the vessel and stirring the mixture. A cationic surfactantand a fatty acid and/or a long or short chain alcohol are then added tothe vessel, and the stirring rate is increased. Stirring is continueduntil a homogenous mixture is formed. The mixture is then left to coolto ambient temperature, under continuous stirring. Optionally perfumeand/or a polymeric structurant (such as disclosed in WO99/43777) is thenstirred into the mixture.

[0261] A suitable microemulsion is prepared by mixing under lowagitation an oil, a solvent such as a low molecular weight alcohol, adispersibility aid such as a nonionic surfactant, a cationic surfactantand 10% by weight or less of water until a clear composition is formed.In order to assist formation of the clear microemulsion, the mixture maybe heated as required. Perfume may optionally be added to the mixture atany stage.

[0262] A suitable a concentrated emulsion is prepared by heating waterto a temperature above 50° C., adding an emulsifier, premixing acationic surfactant, nonionic surfactant and oil and adding this to thewater. Optionally the product is milled and then allowed to cool. Oncebelow 50° C., perfume may be added.

[0263] Product Form

[0264] The water soluble package is preferably in the form of a capsulewhich contains but does not interact with the fabric treatmentcomposition. A suitable alternative is a package comprising a polymericmatrix which incorporates the fabric treatment composition.

[0265] Composition pH

[0266] When the fabric treatment composition is dispersed in water, thesolution preferably has a pH of from 1.5 to 5.

[0267] Product Use

[0268] In a preferred method of use, the water soluble package is placedin the drum of the washing machine at the beginning of the wash cyclefor dissolution and/or dispersion at the beginning of or during therinse cycle.

EXAMPLES

[0269] The invention will now be illustrated by the followingnon-limiting examples. Further modification within the scope of thepresent invention will be apparent to the person skilled in the art.

[0270] Samples of the invention are denoted by a number and comparativesamples are denoted by a letter. All amounts are % by weight based onthe total weight of the composition unless otherwise stated.

Example 1 Preparation of Polymeric Material

[0271] A 10 wt % solution of PVOH in water was prepared by placing 10 gPVOH (Mowiol 20-98 (trade name), ex Kuraray Specialities) and 900 gdemineralised water into a flask and heating to 70° C. To this, 10 ml ofhydrochloric acid (36% aqueous solution) was added to catalyse thereaction and then butyraldehyde was added. The mixture was then stirredat 70° C. for 5 hours under an inert atmosphere, after which time theheating was stopped and agitation continued for a further 20 hours atroom temperature. The reaction mixture was then brought to a pH of 7using a sodium hydroxide solution.

[0272] The resulting solution was precipitated into acetone to yield theacetalised PVOH polymer and washed repeatedly with acetone (500 ml) andthen water (50 ml). It was then dried under vacuum at 70° C. overnightto yield a white polymer.

[0273] The polymer was analysed by H NMR in d DMSO.

[0274] The following peaks were observed: Assignment (see Peak p.p.mGroup Integral structure below) 4.2-4.8 Hydroxyl 0.9746 A, B, C, J 3.8Proton 1.0000 D 3.4 Water 0.8219 2.5 d⁶ DMSO 0.1181 1.8 Methyl onacetate^(a) 0.0529 E 1.2-1.6 Proton 2.2762 F, G 0.9 Methyl 0.1609 H

[0275] This is believed to correspond to the structure:

[0276] wherein the average number ratio of z to x is within the range offrom 1:30 to 1:14, and y is from 1-5%.

[0277] The degree of acetalisation was calculated from the number ofhydroxyl pairs as follows:

[0278] H, which represents the “CH₃” group from the acetal product, wasfound by integration to be 0.1609.

[0279] Therefore the number of acetal repeats each containing an OH pairwas 0.1609/3 or 0.0536.

[0280] A, B and C represent the number of free OH groups. J represents ahydrogen from the acetal ring. A, B, C and J combined is 0.9746.

[0281] The total integration due to A, B and C is 09746—J or0.9746-0.0536, i.e. 0.921.

[0282] The total number of OH repeat units that remain unreacted is0.921/2 or 0.4605.

[0283] Accordingly, the degree of acetal content with respect to thetotal number of OH pairs available is 0.0536/(0.0536+0.4605)*100 or10.43% acetal with respect to OH pairs available.

[0284] Preparation of Polymeric Film

[0285] The poly(vinylalcohol)-butyral (PVA-BA) resin prepared in example1 was diluted to a 7% m/m. solution with demineralized water. Theresulting solution was poured onto a PTFE glued-sheet tray. The polymersolution was then left to evaporate to produce films. The thickness ofthe films was adjusted by increasing or decreasing the volume of liquidpolymer dosed in a given space. After 2 to 3 days, the films were peeledaway from the PTFE tray, and an average thickness was measured at 5regions of the cast films using an electronic micrometer. The films werethen stored at 23° C. and 50% relative humidity for 2 days prior toevaluation.

[0286] The following examples illustrate the effect of anionic/nonionicsurfactant concentration on the butyraldehyde-derivatised PVOH. Theslide-test method described below was employed as a screen for thepolymer films.

Example 1 Film Rupture Testing

[0287] The evaluation of the effect of anionic/nonionic surfactantconcentration on the polymer material is made based on its dissolutionand erosion characteristics using a slide-testing regime.

[0288] This is denoted by the rupture time, i.e. the first time when thepolymer breaks and the contents flow from the inside of the sachet intothe surrounding liquid.

[0289] A film slide was used to hold a 30 mm×30 mm film cast to athickness of 100-200 μm, in place. The slide and film were then immersedin either a detergent surfactant solution or tap water in a 1 litrebeaker. The slide and film to be tested were stirred at ambienttemperature at 293 rpm until the polymer film ruptured.

[0290] The nature of the films tested is given in the table below. TABLE1 Sam- ple Film thickness^(a) Base^(b) Degree modified^(c) Solids^(d)mPa.s^(e) 1 184 20-98 9 15.53 20.6 2 150 20-98 11 15.6 20.8 3 Notmeasured 20-98 12 15.7 21.1 4 192 26-88 10 15.46 23.4 5 173 26-88 1215.6 26.2 6 149 28-99 10 10.83 24.2 7 166 28-99 11 10.75 25.6 8 11028-99 12 10.81 24.11 9 185 20-98 10 15.6 20.7

[0291] The results are given in the table below. TABLE 2 Rupture RuptureCloud Precipitation time in time in Sample point^(a) point^(b)Detergent^(c) water^(d) T_(W)/T_(T) ^(e) 1 <25 46 29 20 1.5 2 <25 37 366.5 5.5 3 <25 35 — — — 4 <25 31 7 5 1.4 5 <25 28 0.25 4 0.07 6 34 40 2515 1.7 7 32 38 20.3 2.8 7.25 8 29 34 13 10 1.3 9 <25 42 60 7 8.57

[0292] The polymer of sample 9 was cast to a thickness of 200 μm andplaced onto a slide. The effect of altering the concentration of apremium washing detergent (Ultra-Wisk, trade name) was then measuredusing the slide test regime at ambient temperature, as described above.

[0293] The results are given in the following table. TABLE 3Detergent^(a) g/L Rupture Time, minutes 0  7 0.008 13 0.016 18 0.035 291.66 65

[0294] The results clearly show that the rupture time variessignificantly with level of detergent.

[0295] A sample of polymer 9 was cast to 90 μm from a 15% solution. Theresulting film was conditioned at 20° C. and 65% R.H. for 24 hours. ATergometer was filled with 1 litre of cold Wirral water (15-20° FH)optionally containing 2 g/litre of Wisk solution (Wisk purchased fromthe U.S. May 2003) and set to agitate at 75 r.p.m. Immediately afteragitation was started the film was placed in the pot, and visuallyinspected for fragmentation (inspection was stopped after 15 minutes).The test was repeated 3 times. The results are given in the followingtable: TABLE 4 Film Time to fragment Sample weight (g) Solution(minutes) 1 0.47 A >15 2 0.38 A >15 3 0.45 A >15 4 0.39 B    3 5 0.42 B   7 6 0.53 B    4

[0296] Fragmentation occurs when the polymeric film breaks into morethan one piece.

[0297] Evaluation of Derivatising Groups

[0298] Films were cast using the polymer of sample 9 and various levelsof butyral derivatising groups (prepared as described above). The slidetest method was used to measure the rupture time in detergent (T_(W))and the rupture time in water (T_(T)).

[0299] The results are given below. TABLE 5 % Butyral T_(w) MinutesT_(T) Minutes T_(w)/T_(T) 6 20  6 3.33 9.3 40 16 2.5  12.5 45 13 3.46

[0300] The results demonstrate that a degree of modification above 6% ofbutyral significantly increases rupture time.

[0301] Evaluation of Mixed Derivatising Groups

[0302] The polymer of sample 9 was reacted as previously described withbutyraldehyde and propioaldehyde. The level of butyral groups was 9%.Levels of propional groups between 0 to 1.4% were used. Slide testing asdescribed above was carried out in 1.66 g/L Wisk. The results are givenin the following table. TABLE 6 % Butyral % Propional Rupture timeSample groups groups (Tw) 1 9 0   60 2 9 0.5 45 3 9 0.7 25 4 9 1.4 18

[0303] The results demonstrate that the presence of propional groupsdecreased the time taken for rupture to occur.

[0304] Viscosity Evaluation

[0305] The sample 9 polymer was diluted to 7% using either demineralizedwater or 20 g/litre SDS. The viscosity of the diluted resin was thenmeasured.

[0306] The results are given in the following table. TABLE 7 SDS g/LViscosity, mPa · s^(a)  0 230 20 970

[0307] The results demonstrate that the anionic surfactant isinteracting with the polymeric film to create a gel-like structure.

[0308] Film Thickness Evaluation

[0309] The effect of film thickness on the rupture time in tap-water offilm prepared from the sample 9 polymer was evaluated.

[0310] Films of various thickness were placed onto the slide andruptured, according to the slide test regime described above.

[0311] The results are given in the table below. TABLE 8 Film thickness,μm Rupture time, minutes^(a) 110  8 180 10 300 70 550 85

[0312] As can be seen the release times can be altered to suit theenvironment of use e.g. thickness and surfactant concentration can becoupled to decrease or increase active release.

[0313] Evaluation of Plasticiser

[0314] The sample 9 polymer was formed into films according to themethod described above in the presence of various concentrations ofsorbitol. The rupture time at ambient temperature in tap-water wasevaluated using the slide test regime.

[0315] The results are given in the following table. TABLE 9 %Sorbitol^(a) Rupture time, mins. 0 15 0.1 10 5.0  7 10  4

[0316] Evaluation of Enzymes

[0317] It is undesirable for enzymes in washing formulations to have anysignificant effect on the time at which rupture occurs.

[0318] Films were cast from the sample 9 polymer, as above, and immersedin an enzyme-containing premium detergent (Persil Performance, tradename), and an enzyme-free detergent (Persil Non-Biological liquid) at 8g/litre of water. The rupture times were measured using the slide testregime.

[0319] The results are given in the following table. TABLE 10 DetergentProduct Concentration, g/L Rupture time, mins None N/A 10 Persil Non- 8120 Biological Persil 8 120 Performance

[0320] The results illustrate that the enzymes in the liquids had noadverse effect on the rupture time.

[0321] Evaluation of Cationic Surfactant

[0322] A cast film of the sample 9 polymer was screened using theslide-test regime as described above in the presence of varyingconcentrations of cetyltrimethylammonium chloride (CTAC).

[0323] The results are given in the following table. TABLE 11Concentration of CTAC (g/L) Rupture time (mins) N/A 30 0.2 28 2.0 30

[0324] It can be seen that varying the concentration of the cationicsurfactant has substantially no effect on the time of rupture.

[0325] Evaluation of pH Variation

[0326] A film of the sample 9 polymer cast at 200 μm thickness wasevaluated for rupture time in tap-water at various pH levels. Theresults are given in the following table. TABLE 12 pH (adjusted withHCl) Rupture time (minutes) 6 8 1.3 7

[0327] Evaluation of Film in Laundry Operation

[0328] Capsule Preparation

[0329] The sample 9 polymer was cast to form a film measuring 10 cm×10cm and a thickness of 50 μm, 90 μm or 100 μm. This was folded in halfand 3 of the 4 sides were heat sealed at 150° C. using a Hulme-Hunterheat sealer to form a pouch. 20 g of a formulation consisting of 96 wt %Tetranyl AOT-1 (a quaternary ammonium softening material based ontriethanolamine, 80% active ex Kao) and 4 wt % perfume (hereinafterreferred to as formulation “A”) or 20 g of a formulation comprising 96wt % Tetranyl AOT-1, 3 wt % water and 1 wt % perfume (hereinafterreferred to as formulation “B”) was then introduced into the pouch, andthe top of the film sealed to form a capsule. The capsule was thenstored at 23° C. and 50% relative humidity for 2 days prior toevaluation.

[0330] Machine Wash Evaluation

[0331] A top-loading washing machine (Whirlpool) was filled with 65litres of water (60 French Hardness at 15° C.). 110 g washing liquid(Ultra Wisk) was added and gently agitated for 10 minutes untildissolved. 3.5 kg of a mixed ballast load comprising 1 kg Terry towel, 1kg cotton poplin, 1 kg poly-cotton and 0.5 kg polyester was then added,together with ten 20 cm×20 cm Terry towel monitors, followed by thecapsule formed from a 100 μm thick film containing formulation “A”. Themachine was then set for an 18 minute wash at 15° C., a spin, and onerinse (5 minutes). After the wash phase the integrity of the capsule wasassessed visually, and found to be very flaccid but still intact. Afterthe programme was finished, the cloth and drum were inspected for anyresidual gelled polymer film. No residual film was found.

[0332] Softness Evaluation

[0333] The Terry towel monitors were retrieved and softening wasassessed after tumble drying against the tumble-dried controls by atrained panel of 10 people using paired comparison testing. Results wereanalysed at the 95% C.I. level.

[0334] The results are given in the following table. TABLE 13 Treatment% Preference Detergent only 22 Detergent & capsule 78

[0335] The results clearly indicate that softening benefits wereperceivable when the capsule was present.

[0336] Perfume Evaluation

[0337] The Terry towelling was also assessed by the panel (pairedcomparison test) for perfume preference both on damp cloth (5 hrs linedried) and after tumble drying.

[0338] The results are given in the following table. TABLE 14 Treatment% Preference Detergent only-assessment before 21 tumble drying Detergent& capsule-assessment before 79 tumble drying Detergent only-assessmentafter 20 tumble drying Detergent & capsule-assessment after 80 tumbledrying

[0339] The results clearly indicate that significant improvements inperfume benefits are achieved when the capsule is present in the laundrytreatment process.

[0340] The investigation for gelled residue was conducted on a further 3occasions, under the machine washing conditions described in the exampleabove. On all three occasions no residue was found either on the cloth,drum or agitator spindle.

[0341] Further Evaluation in Laundry Operation

[0342] A Whirlpool U.S. top-loader was filled with 2.5 Kg of mixedballast (Terry towel, poly-cotton, poly-ester, cotton sheeting) with 6terry towel monitors (20 cm×20 cm). The machine was allowed to fill with65 litres of cold water at 15° C., and 6° F.H. 110 g of ultra-Wisk wasadded. A 10 or 18 minute super-wash was selected followed by a singlerinse and spin. The capsules comprising formulation “B” andunencapsulated fabric treatment compositions were added at variousstages of the laundry cycle. After the cycle was complete the ballast,and the monitors were dried in a Whirlpool U.S. dryer. The monitors werethen isolated, and treated with bromophenol blue stain in order toindicate the intensity and evenness of cationic softener coverage.

[0343] The bromophenol blue test consisted of bromophenol blue dye (0.7g) dissolved in ethanol (10 g), added to hot water (5 ml) and then addedto 10 litres of cold Wirral water (final pH 7.4).

[0344] The monitors were added to the bromophenol blue solution, left atambient temperature for 15 minutes with occasional agitation and thenrinsed gently until the rinse waters were clear. The clothes were thenspun for 30 seconds to remove any excess water, and left to line dryaway from direct sunlight.

[0345] The monitors were then visually assessed via a trained panel of 8people for evenness of deposition on a scale of 1-5 where 1 denotes verypatchy and 5 denotes complete coverage, and intensity of blue stain alsoon a scale of 1-5 where 1 denotes very pale and 5 denotes very dark.

[0346] In the following table, the capsule was formed from a film castto 50 microns and the 18 minute wash cycle was used. TABLE 15 TreatmentEvenness Intensity Capsule containing 20 g formulation 3 4 “B” added atstart of wash cycle 20 g formulation “B” added at start 4 4 of rinsecycle 20 g formulation “B” added at start 1 1 of wash cycle 30 mlUltra-Snuggle added at start of 5 4 rinse cycle Capsule containing 20 gformulation 1 1 “B” ruptured by hand and added at start of wash cycle 20g formulation “B” pre-dispersed in 5 4 200 ml of demineralised water andadded at start of rinse cycle

[0347] In the following table, the capsule was formed from a film castto 90 microns and the both the 10 and 18 minute wash cycles were used.

[0348] Softening was assessed by a trained panel of 6 people on a linescale of 0 to 100 where 0 denotes not at all soft and 100 denotesextremely soft. The results were analysed using Anova and Tukey-KramerHSD statistics. Perfume was assessed by a trained panel of 8 people on ascale of 0 to 5 where 0 denotes no perfume and 5 denotes very intenseperfume. Perfume assessment was made on the wet fabrics immediatelyafter removal from the washing machine and also 24 hours after removalfrom the tumble dryer. TABLE 16 Perfume Perfume Treatment Softening(wet) (24 Hrs) 30 ml Ultra-Snuggle 59.2 2.25 1.88 added to start ofrinse cycle after end of 18 minute wash cycle Capsule containing 20 g64.1 2.33 1.98 formulation “B” added at start of 18 minute wash cycleCapsule containing 20 g 45.3 2.24 1.67 formulation “B” added to start ofrinse cycle after end of 18 minute wash cycle

[0349] Evaluation of Plasticisation Via the Formulation

[0350] A plasticiser for PVOH films, PEG1500, was added to formulation“B” which was then packaged in a film formed of the sample 9 polymercast to 90 microns.

[0351] Tactile evaluation of the film was made by a trained panel after24 hours storage at 20° C. and 60°R.H.

[0352] The results are given in the following table. TABLE 17 Sample 1 2Tetranyl 96  94  AOT-1 Water 3 3 PEG1500 (1) 0 2 Perfume 1 1 Feel Hardcrispy Soft, very capsule pliable

1. A water soluble package comprising a polymeric film, the polymeric film comprising a polymeric backbone derived from a polymer which is water soluble, as defined herein, and one or more derivatising groups attached to the backbone, the derivatising group(s) being derived from a parent material having a ClogP of from 0.5 to
 6. 2. A water soluble package comprising a polymeric film, the polymeric film comprising a polymeric backbone derived from a polymer which is water soluble, as defined herein, and one or more derivatising groups attached to the backbone, the derivatising group(s) being derived from a parent material comprising a C4 to C22 hydrocarbyl chain.
 3. A water soluble package comprising a polymeric film, the polymeric film comprising a polymeric backbone derived from a polymer which is water soluble, as defined herein, and one or more derivatising groups attached to the backbone wherein the package has a relative rupture ratio of greater than 1, more preferably greater than 3 most preferably greater than
 7. 4. A water soluble package as claimed in claim 1 comprising a crystallinity disrupter and/or a plasticizer physically or chemically bound to the backbone of the polymeric film.
 5. A water soluble package as claimed in claim 1 wherein the polymer has a solubility or dispersibility in anionic or combinations of anionic/nonionic surfactants of more than 15 minutes when the surfactant concentration in water is greater than 0.05 g/L and a solubility or dispersibility of less than 15 minutes when the surfactant concentration in water is less than 0.05 g/L.
 6. A water soluble package as claimed in claim 1 wherein the polymeric backbone is derived from PVOH.
 7. A water soluble package as claimed in claim 1 wherein the parent material from which the derivatising group is obtained is selected from the group consisting of acetals, ketals, esters, fluoro-organics, ethers, epoxides, alkanes, alkenes and aromatic compounds.
 8. A water soluble package as claimed in claim 1 wherein the parent material from which the derivatising group is obtained is an aldehyde.
 9. A water soluble package as claimed in claim 1 wherein the polymer has an average degree of saponification of from 70 to 99%, more preferably from 80 to 99%, most preferably from 88 to 99%.
 10. A water soluble package as claimed in claim 1 wherein the degree of derivatisation of the polymeric backbone by the derivatising group is from 0.1 to 40% by weight, based on the total weight of the polymer, more preferably 2 to 30%, most preferably 5 to 15%, e.g. 8 to 12%.
 11. A water soluble package as claimed in claim 1 wherein the polymer is based on PVOH and the number ratio of the derivative groups to the free hydroxyl pairs on the backbone is from 1:3 to 1:30, more preferably 1:4 to 1:20, most preferably 1:7 to 1:15, e.g. 1:8 to 1:13.
 12. A water soluble package as claimed in claim 1 wherein the polymeric film is capable of forming, upon contact with a detergent surfactant in a micellar or liquid crystalline form, a gelled network having a viscosity or an apparent molecular weight greater than the molecular weight of the polymeric film alone.
 13. A process for conditioning fabrics comprising the steps of adding to a laundry cycle of a washing machine the water soluble package according to any one of the preceding claims and contacting the contents of the package with fabric in the drum of the washing machine.
 14. A process according to claim 13 wherein the tendency of the water soluble package to break down is reduced in the presence of a fabric wash detergent active. 